Influence of Varying Hard Segments on the Properties

of Chemically Crosslinked Moisture-Cured

Polyurethane-Urea
D. K. CHATTOPADHYAY,1 B. SREEDHAR,2 K. V. S. N. RAJU1
1
Organic Coatings and Polymers Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
2
Inorganic & Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India

Received 22 February 2005; revised 4 June 2005; accepted 8 June 2005

DOI: 10.1002/polb.20586
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Polyurethane prepolymers are widely used in the reactive hot melt adhe-
sives and moisture-cured coatings. The chemically crosslinked moisture-cured formu-
lation based on PEG-1000 and isophorone diisocyanate was prepared with NCO/OH
ratio of 1.6:1.0. Trimethylol propane was used as a crosslinking agent. The excess iso-
cyanate of the prepolymer was chain extended in the ratio of 2:1 (NCO/OH) with dif-
ferent aliphatic diols, and 4:1 with different aromatic diamines. The polymer network
maturation during moisture cure was followed by dynamic mechanical thermal ana-
lyzer (DMTA) instrument. The thermal and dynamic mechanical properties of the
crosslinked polymers were evaluated using thermogravimetric analysis, differential
scanning calorimetric analysis and DMTA. Surface properties were evaluated through
angle-resolved X-ray photoelectron spectroscopy.
The present article discusses the physical properties of moisture-cured polyur-
ethane-urea (MCPU) containing chemical crosslinks in the hard segment. The com-
plete moisture-cured polymers showed amorous results toward room temperature
modulus, tensile strength, hardness, thermal stability, and transparency. The surface
properties showed the enrichment of soft segments. V C 2005 Wiley Periodicals, Inc. J

Polym Sci Part B: Polym Phys 44: 102–118, 2006

Keywords: coatings; crosslinking; mechanical properties; polyurethane; thermal
properties

INTRODUCTION molecular weight of the macrodiol, whereas the

Segmented polyurethane ureas are block copoly-
mers with alternating soft and hard blocks,
which because of structural differences, separate
into two phases. The soft segments are derived
from a macrodiol and hard ones are the reaction
product of diisocyanate and a chain extender.
The length of the soft segment results from the
Correspondence to: K. V. S. N. Raju (E-mail: kvsnraju@
iict.res.in)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 44, 102–118 (2006)
V
C 2005 Wiley Periodicals, Inc.
102
length of the hard segment depends on the kind
and molar ratio of the compounds used in the
reaction. Hard segment plays the role of physi-
cal crosslinks and acts as a higher modulus filler
in the low modulus soft matrix, whereas the soft
phase gives extensibility to the polymer.1 In the
last few decades, researchers have systemati-
cally varied the chemical composition, structure,
and molecular weight of both the soft and hard
segment components of segmented polyureth-
anes to modify their properties as well as to
gain an insight into the basic structure–property
relationships. In the case of soft segments, most
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU
of the work has focused on polar low molecular
weight macrodiols such as polyethers or polyest-
ers. On the other hand, hard segments are cre-
ated from aromatic/aliphatic/cycloaliphatic diiso-
cyanate chain extended with low molecular weight
diols or diamines. Although such studies provide a
good understanding of key structural features that
determine the mechanical behavior of polyur-
ethane, the incredible variety found in the mor-
phologies and superstructures, which arise due to
the change in morphology of the resultant materi-
als, for a particular structural variation makes it
extremely difficult to assess the relative impor-
tance of the variable factor.
For thermoplastic polyurethane elastomers,
hard segments are usually associated with rela-
tively weak secondary bonds and hence significant
deterioration of the mechanical properties occur as
the working temperature approaches softening or
melting temperature of the hard domains. There-
fore, controlled crosslinking through chemical
bonds at the hard segment not only improves the
working temperature range but also improves the
mechanical and thermal properties of the poly-
mer.2–7 It is, for instance, of great practical and
theoretical importance to know the effect of che-
mical crosslinks on their properties. Crosslinks
increase the structural integrity of the hard seg-
ment by creating permanent crosslinks between
the hard segments. This prevents extensive dis-
ruption and reorganization of the hard domains
from taking place during the stress/strain or wear
generated while service condition.3 The chemical
crosslinks have been introduced into the samples
in a variety of ways, and studies have been at-
tempted to examine the effects of chemical cross-
linking on the material properties of polyurethane
elastomers. Some systems contain triols or higher-
functional polyols,8–13 isocyanates with functional-
ities greater than two,5,14 NCO/OH ratios greater
than one,2,11–13,15,16 or combinations thereof.2,11–13
Many of these studies have focused on the tensile
and mechanical properties of the polymers.2,5,8–17
In addition, the effects of crosslinking on swel-
ling,2,5,8,12–15,17 thermal degradation,10,14,16 ther-
mal properties,2,5,14,17 and morphology13,14,16 have
been examined.
Researchers also have attempted to examine
the influence of hard segment cohesiveness on
the thermomechanical properties of segmented
polyurethane by introducing chemical crosslinks
into the hard segment. Various crosslinking agents
(CLAs) such as peroxides and trifunctional chain
extenders have been utilized to chemically modify
103
the hard domain cohesiveness, using chemical
crosslinks.8,15,18–20 In all cases, however, this ap-
proach results in significant modifications of the
packing and organization of the hard segment.
Crosslinking has also been accomplished by uti-
lizing an excess of the diisocyanate component to
promote biuret- and allophanate-type linkages.21
In such case, in addition to variations in the hard
segment packing and organization, the presence
of additional hard segment material due to biuret
and allophanate also changes the hard segment
volume fraction and hence the interconnectivity
of the hard segment. In addition to chemical
crosslinking, increased hard segment intermolec-
ular interactions can also be obtained by utilizing
hard segments with stronger nonbonded interac-
tions, i.e., by improving the polarity of the hard
domains. For example, significant improvements
in many of these properties sensitive to weak
interchain forces within the hard domains were
obtained by introducing more strongly associated
polar groups into the hard segments such as urea
linkages, which increase the hard domain soften-
ing temperature because of the enhanced forma-
tion of hydrogen bonding structure. While work-
ing with polyester–urethane, Chang et al.3 have
varied the hard segment crosslink density by
varying the butane diol to trimethylol propane
(TMP) ratio and examined its effect on physical
and mechanical properties. Petrovic et al.4 have
reported the effect of chemical crosslinking on
the properties of the polyether–urethane. Buckley
et al.22 and Nallicheri et al.23 reported that there
is no change in morphology after crosslinking of
unsaturated systems by solid-state irradiation,
and increasing crosslinking in the hard segment
increases the modulus, decreases elongation at
break, and the ultimate strength went through
a maximum. Sample morphology is affected by
many factors, such as the chemical nature of the
components, stoichiometric ratio between the two
segments, molecular weight and distribution of
the segment, synthetic method used in the pre-
paration of the polymer, and on the thermal
treatment used before the characterization.24,25
The presence of different amount of phase sepa-
ration and phase mixing characteristics within a
polyurethane sample complicated the understan-
ding of its morphology and superstructure. There-
fore, the qualitative and quantitative evaluation
of degree of phase separation or phase mixing26–29
and factors affecting the phase separation, such
as chemical structure,30,31 molecular weight27,32 and
functionality of component2–4 and hydrogen bond
104 CHATTOPADHYAY, SREEDHAR, AND RAJU
between segments,5,33,34 have been widely studied.
In crosslinked polyurethane-urea as in our study,
two factors are responsible for different amount of
hard segment cohesion. First, the phase separa-
tion process associated with different chain ex-
tender structure, and second, is the phase mixing
process generated from the solid-state postcure
process.
The solid-state polymerization of moisture-
cured polyurethane-urea (MCPU) takes place
mainly by diffusion-dominated mechanism. The
reaction proceeds through a carbamic acid inter-
mediate, and the latter dissociates to yield car-
bon dioxide and an amine, which further reacts
with another isocyanate to produce urea link-
ages.35–37 The solid-state polymerization results
in microphase mixing and crosslinking, and
increases the rigidity of the polymer. The rate of
polymerization depends on factors like relative
humidity (RH) in the environment, chain ex-
tender structure that influence the state of
packing and organization of the hard segment,
the type of catalyst and its concentration, pres-
ence or absence of biuret and/or allophanate
formation, temperature and so forth. Since the
formation of CO2 due to the decomposition of
carbamic acid may adversely affect film proper-
ties, if trapped in the film, it is therefore neces-
sary to have an optimized humidity level.38–41
Formation of side products like biuret and allo-
phanate42 both in liquid-state polymerization
and solid-state postcuring reaction greatly influ-
ence the coating properties. For example, these
functions enhance the adhesion43 and thermal
stability.44,45 However Dusek et al.46 reported
that formation of biuret is much faster than that
of allophanate, and at low temperature (
60 8C)
formation of biuret and allophanate is very slow.
Petrovic and Javni47 reported that synthesis in
solution results lower molecular weight because
of the lack of side reactions that cause branch-
ing. The formation of side products can be mini-
mized, to obtain good mechanical properties, by
careful control of moisture levels.
The strong industrial interest in polyurethane-
urea polymers has spurred ongoing investigations
into their structure–property correlation. Despite
significant improved device performance of MCPU,
a number of scientific challenges remain to be fully
understood and quantified to predict the behavior
of MCPUs. For example, the dependence of coating
performance on the phase mixing and the factors
affecting the development of phase-separated struc-
tures are still poorly understood. The present article
is a step forward toward understanding the phase-
separation/phase-mixing imbalance with the varia-
tion of chain extender structure.
EXPERIMENTAL
Materials
PEG-1000, TMP, isophorone diisocyanate (IPDI)
(mixture of Z and E isomer in the ratio of 3:1), 4-
aminophenyl disulfide (DIS), 2,2-diethyl-1,3 pro-
panediol (DIE), and 4,40 -diamino-diphenyl meth-
ane (MET) from Aldrich Chemicals (Milwaukee,
WI), 4,40 -diamino-diphenyl sulfone (SUL) from
Fluka Chemicals (Buchs, Switzerland), 1,4-
butanediol (BD) from Spectrochem Pvt. Ltd. (Mum-
bai, India), propane-1,2-diol (PD), 2-ethoxyethyl
acetate, and sulfur-free toluene from S.D. Fine
Chemicals (Mumbai, India) were used. Solvents
were stored over activated 3–4 Å molecular sieves.
Method
The resin kettle was equipped with a dropping
funnel, stirrer, thermometer, reflux condenser,
and a nitrogen inlet. An excess amount of IPDI
was taken so as to get NCO:OH ratio of 1.6:1.0.
About 50 g PEG and 9 g TMP mixture was
added to the kettle at 60–70 8C and the reaction
was continued at 75–85 8C for 6 h in absence of
catalyst. The synthesized isocyanate-terminated
prepolymer was chain extended in the ratio 2:1
(NCO/OH) with different aliphatic diols, and 4:1
with different aromatic diamines in the presence
of 0.05 wt % dibutyl-tin diluarate and 0.05 wt %
triethylamine catalysts. The polymers were casted
on a smooth surface of tin foil by using a power-
driven automatic applicator and cured at room
temperature and humid condition for more than
2 months, and then the supported polymers were
placed in a clean mercury bath to amalgamate
the tin substrate. Mercury or amalgam adhering
to bottom side of the unsupported film was
cleaned off. The free films were used for thermal,
angle resolved X-ray photoelectron spectroscopy
(AR-XPS), and dynamic mechanical measure-
ments. TAGOSTABTM BF2370 (Goldschmidt) sur-
factant with concentration 0.05% was used to
prepare uniform film for tensile test.
For the cure study, casted films were amalga-
mated after complete solvent evaporation or re-
moval of tackiness, and the free film was kept in
a suspended position at a temperature of 25 8C
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU
and a relative humidity (RH) of 45–50%. The
samples were coded with the chain extender
name as given in bracket in material section, with
prefix PU, and suffix-1, for example, PUSUL-1 for
polyurethane with 4,40 -diamino diphenyl sulfone
as chain extender. The 100% moisture-cured for-
mulation without any chain extender was named
as PUIT-1, and PUSUL-1 HT represents the heat-
treated PUSUL-1 sample. The heat treatment
was carried out at 100 8C for 1 h under reduced
pressure in an oven.
FTIR Instrumentation
The prepolymer was diluted with solvent and
the thin coatings of the polymers on dried KBr
(Fluka) pellets was performed and cured com-
pletely. Fourier transform IR spectra (FTIR) of
the crosslinked PU-urea films were obtained
using a Nicolet Nexus Spectrometer. Each sam-
ple was scanned 128 times with a resolution set-
ting of 2 cm1 and averaged to produce each
spectrum. Using the Nicolet software, the area
A of the NCO band was calculated with respect
to a baseline drawn between the points at 2400
and 2150 cm1. Curve-fitting simulations were
performed using Origin software program. The
m (NH) and m (C¼ ¼O) band were deconvoluted
considering peaks as Gaussian with a number of
iteration to get the best-fit Gaussian peaks.
Dynamic Mechanical Analysis
Dynamic mechanical thermal analysis (DMTA)
IV instrument (Rheometric Scientific, USA) in
tensile mode at a frequency of 1 Hz and with a
heating rate of 3 8C/min was used to determine
the viscoelastic behavior of the polymers (15 
10  0.15 mm3) in nitrogen atmosphere, and the
temperature range of study was from 50 to 150 8C.
To evaluate cure behavior, a number of samples
were run periodically at different time intervals
and in the temperature range 35–150 8C.
Thermal Properties
The thermal properties of polymer films were
studied using Mettler Toledo TGA/SDTA 851e and
DSC 821e thermal systems (Zurich, Switzerland).
For TGA, films were cut into small pieces and
about 20 mg of sample was taken and heated at
a constant rate of 10 8C/min in nitrogen from
30 to 600 8C with N2 flow rate of 30 mL/min.
Different heating rates were used to study the
105
thermooxidative stability of some selected samples,
with O2 flow rate of 30 mL/min. For the DSC
study, about 20 mg of samples were placed in the
aluminum pan, sealed properly, and scanned in
the temperature range 60 to 200 8C at a heating
rate of 10 8C/min in nitrogen atmosphere (flow rate
30 mL/min).
Tensile Properties
Tensile properties of the polymer films were
measured by Universal Testing Machine, AGS-
10k NG (Shimadzu, Japan) at 25 8C and 50%
humidity. The test specimens were in the form
of dumbbells, according to ASTM standard and
procedure D-638. The gauge length was 50 mm
and crosshead speed of 20 mm/min. The data
reported are the average of five measurements.
XRD Studies
The X-ray diffraction (XRD) intensity was
recorded as a function of diffraction angle using
a Siemens/D-5000 diffractometer with Cu Ka ra-
diation and k ¼ 1.5406 Å. Film specimens were
cast from cellosolve acetate solution and had a
thickness of 0.1–0.15 mm.
XPS Measurements
The surface of the samples was analyzed using
a KRATOS AXIS 165 X-ray photoelectron spec-
trometer. The X-ray gun was operated at 15 kV
and 20 mA. Survey and high-resolution spectra
were obtained using 80 and 40 eV pass energy,
respectively. The analyzer chamber was degasi-
fied and pressure in the analyzer chamber was
kept at 108 Torr. A thin film of thickness
0.15 mm was used for XPS analysis. The sample
was tilted in such a way so as to change the
angle h between the normal to the sample and
the analyzer. At h ¼ 08, the sample was perpen-
dicular to the detector, leading to the maximum
sampling depth. The effective sampling depth, z,
was derived by z ¼ 3k cos h, where k is the effec-
tive mean free path for electrons to escape from
the surface and was set to the value of 2.5 nm.
Therefore, at h ¼ 08, z ¼ 7.5 nm, and at h ¼ 808,
z ¼ 1.3 nm.48 All spectra are presented charge
balanced and energy referenced to C 1s at
284.6 eV. Spectra were deconvoluted using San
Solaris based Vision 2 curve resolver. Symmetric
Gaussian shapes were used in all cases.
106 CHATTOPADHYAY, SREEDHAR, AND RAJU
Scheme 1. Cure reaction in the solid state during network advancement.
RESULTS AND DISCUSSION
The synthesis of high solid isocyanate-termi-
nated polyether-urethane was carried out using
IPDI (mixture of Z and E isomer in the ratio of
3:1), which has two different reactive NCO ter-
minals in the absence of catalyst. The solvent
used in the present investigation was 2-ethoxy-
ethyl acetate. Secondary isocyanate group of
IPDI was more reactive than primary isocyanate
group in the absence of catalyst because of the
steric and stereoelectronic factors as observed
earlier.49 The synthesized polymer was chain
extended and cured in the presence of a mixture
of catalyst as reported in the Experimental sec-
tion. The chain-extended polyurethanes were
subjected to dynamic mechanical, thermal, XRD,
and XPS analysis. Tensile strength and % elon-
gation were also determined. The main aim of
this paper was to understand with reasonable
precision how the chain extender structure gov-
erns the film properties of moisture-cured poly-
urethane. TMP was introduced as a CLA, to
increase the mechanical integrity, stiffness, and
hardness. The CLA forms highly interconnected
segment morphology, and is capable of opposing
deformation of the microstructure in the pres-
ence of stress and strain.
The curing of MCPU and moisture results in
three-dimensional network formations by form-
ing urea bonds (Scheme 1), and the time of
maturation depends on the percentage RH, tem-
perature, catalyst concentration, amount of ex-
cess isocyanate in the system, rate of diffusion
of water vapor into the sample to form the
amine, and the thickness of the sample. For the
excess NCO group consumption, many more
reactions were suggested, and these are sponta-
neous isocyanate group dimerization at room
temperature, appearance of the allophanate
and/or biuret linkages, and so forth.50 However,
Duff and Macial51 reported that the predomi-
nant postcure process should be because of the
reaction of isocyanate group with atmospheric
moisture to form an amine, which further con-
denses with an additional isocyanate group from
the immediate vicinity to form a urea linkage.
Again, the byproduct formation during the reac-
tion is dependent on the thickness of the film,52
and to minimize side reactions, we used thin
films of thickness 0.1–0.2 mm. The rate of CO2
production during the network maturation may
adversely affect the polymer properties, and can
be controlled by crosslinking conditions, in par-
ticular RH and temperature.38 Excess humidity
may create premature curing and produce de-
fected films. In such case, molecules may not
orient in proper place or the system may lag the
close-packed structure as a result of less cure
time. Again, low humidity may cause the poly-
mer to take longer time for complete curing. So,
it is necessary to optimize the cure conditions to
get the best coating properties. In the present
investigation, RH and temperature were main-
tained within 45–50% and 25 8C, respectively, to
study the cure behavior.
FTIR Spectroscopy
Figure 1(a) shows the decay of NCO group
vibration with increasing cure time for PEG/
TMP/IPDI system. The integrated peak areas
with increasing cure time suggest that more than
30 days is needed to achieve 95% cure, with an
estimating error of 63%. At the same time, the
bands due to urea linkages, namely NH stretch-
ing and deformation bands at 3395 and 1525 cm1,
respectively, increase as crosslinking reactions pro-
gress. The FTIR spectra of the chain-extended
MCPUs are mainly characterized by bands at
3100–3700 cm1 (NH stretching vibrations), 2800–
3000 cm1 (CH stretching vibrations), 1600–
1800 cm1 (C¼ ¼O stretching vibrations), 1540 cm1
(amide II, dNH þ mCN), 1240 cm1 (amide III,
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU 107

Figure 1. (a) The change in spectral intensity of NCO group with cure time for
PEG/TMP/IPDI system, (b) FTIR peak deconvolution of carbonyl band in PUBD-1,
and (c) FTIR peak deconvolution of 
NH zone in PUBD-1.

1
dNH þ mC N), and 1110 cm (COC stretching
vibration, ether group). As the major concern of
this work is to focus on the hydrogen bonding and
their relation to the phase separation of the hard
and soft segments, especially two regions are of
main interest. First, the C¼¼O stretching vibration
from 1600 to 1800 cm1, and second, the NH
stretching vibration from 3100 to 3700 cm1. Peak
deconvulation for all the synthesized polymers con-
firms that the bands assignable to the urethane
group are centered at 1720–1730 cm1 (free
C¼¼O) and at 1707–1711 cm1 (bonded C¼ ¼O),
whereas those assigned to the urea group are cen-
tered at 1665–1680 cm1 (free C¼ ¼O) and at
1644–1655 cm1 (bonded C¼ ¼O). In Figure 1(b),
the peak separation of the IR carbonyl bands by
108 CHATTOPADHYAY, SREEDHAR, AND RAJU
Figure 2. E0 vs. temperature plot of the PU-urea film (PUIT-1) showed the change
of modulus with cure time.
peak deconvolution is shown for PUBD-1. A flat
baseline was chosen for the deconvolution of
C¼¼O and NH zone. For deconvolution study,
the second derivatives of spectra in mC¼ ¼O and
mNH zone was used to find out the number of
Gaussian peaks. The correlation coefficients of
the fitting process were more than 0.999. The
analyzed data (not shown) suggests that the peak
contribution from the hydrogen bonded carbonyls
from urea as well as urethane zone were the
highest for PUSUL-1 and lowest for PUDIE-1.
Among diol chain-extended MCPUs, PUBD-1
shows the more hydrogen bonding property in
both the urethane as well as urea zone. The NH
stretching vibration yields complementary struc-
tural information to the C¼ ¼O stretching vibra-
tion. NH groups can form hydrogen bonding with
C¼¼O groups of the hard segments as well as
with ether groups of the soft segment. Figure 1(c)
shows the deconvoluted FTIR spectra of NH
stretching region for the PUBD-1 film. Since for
stronger hydrogen bonding the frequency shift
(Dm) toward the lower wave number region will
be higher, the NH hydrogen bonded stretching
vibration at 3400 cm1 was assigned as  NH
O¼ ¼C (type 1) and a strong absorption peak cen-
tered at around 3315 cm1 as NHCOC (type
2) hydrogen bonds. The peak contribution of
type 1 and type 2 hydrogen bonding structure in
PUBD-1 suggests that the amount of phase mix-
ing was higher compared with the amount of
phase separation (see the peak area at 3315 and
3400 cm1 in Figure 1(c)). The free NH stretching
vibration appears as a shoulder at about 3485
cm1. The intensity of this shoulder increases
with the increase in branching in the chain
extender structure. For the NH stretching vibra-
tion, the formation of the hydrogen bonds alters
the electronic distribution associated with the
N H bonds. The exact position depends very
much on the strength of the hydrogen bonds
formed, and this bond strength strongly depends
on the local geometry, such as linearity of the
bonds involved and the distance between the
groups.53,54 An overtone of deformation vibration
of NH group increased by Fermi resonance at
3162 cm1 was also observed.55 The deconvoluted
data suggests that PUSUL-1 and PUBD-1 were
more phase separated in comparison with other
diamine and diol chain-extended MCPUs. A more
detailed investigation on the soft, hard, and chain
extender structure on the hydrogen bonding
properties will be presented elsewhere.56
Dynamic Mechanical Behavior
The representative change of modulus plot with
time is shown in Figure 2, and the change in
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU 109

Table 1. Change of Modulus with Maturation Time consequently less tensile strength. With time,
of PUIT-1 (Film Thickness ¼ 0.15 mm) films developed strength as a result of NCO
and moisture reaction. The increasing glass
E0 (106 Pa), E00 (106 Pa), modulus and rubbery modulus to some extent
Cure time at 40 8C at 40 8C
increases the resistance to low-temperature
10 h 2.15 0.61
deformation. When the thickness of the film was
19 h 2.34 0.69 0.1–0.2 mm, it was observed that more than
19 h þ1d 7.86 2.05 30 days is needed to accomplish the saturation
19 h þ2 d 8.5 2.58 curing for the time, temperature, and identical
19 h þ 3 da 17.2 3.09 concentration of catalyst.
19 h þ 13 d 31 7.47 The modulus versus temperature curve with
19 h þ 14 d 36.8 7.98 different chain extender is shown in Figure 3.
19 h þ 22 d 83.5 38.1 The E0 value of PUSUL-1 and PUMET-1 were
a 11.8  107 and 8.4  107 Pa, respectively, at
Cure time: 19 hours and 3 days.
25 8C, as shown in Table 2. At 25 8C, not much
difference of E0 was observed between diol and
the modulus (E0 , E00 ) at 40 8C with maturation diamine chain-extended polyurethanes, but sig-
time is tabulated in Table 1. The tensile storage nificant difference was observed in the glassy
modulus E0 is a measure of the stiffness of a modulus (Fig. 3). The change of glassy modulus
material. The glass state modulus is due to elas- with different chain extender could be due to
tic energy of crystalline and glass state amor- the structural difference of the chain extenders.
phous segment, whereas the rubbery state mod- The diol chain extenders formed urethane bonds
ulus is due to the entropy elasticity owing to the during reaction with NCO, whereas the di-
phase-separated structure of the material. The amine chain extenders formed urea bond on
change of modulus at 40 8C with time depicts reaction with NCO end groups. Urea bond
the increase in crosslink density and phase mix- presents two nitrogen atoms suitable to form
ing characteristics. The increase in modulus is hydrogen bonds, whereas urethane groups pre-
indicative of molecular weight build up of coat- sent one nitrogen in this condition. Conse-
ings because of crosslinking. Initially, the casted quently, the presence of urea groups produced
films after complete solvent evaporation were in an increase in the hard segment cohesion and
very soft condition with less storage modulus more phase-separated structure of the material,
(E0 ¼ 2.15  106 Pa after 10 h at 40 8C), and and thus, increase the rigidity. Furthermore, the

Figure 3. E0 vs. temperature plot of the PU-urea films with different chain extenders.
110 CHATTOPADHYAY, SREEDHAR, AND RAJU

presence of aromatic ring in diamine chain

1,4-Butane

Colourless
PUBD-1

2.21
extenders increases the stiffness to the polymer.

23.9
72.6

43.4
6.5
193.2
161.9

92
diol
Therefore, the substitution of a diamine chain
extender in place of the diol created a larger soft/
hard segment polarity difference and thereby an
enhanced physical crosslinking and/or filler

1,3 propane
2,2-Diethyl- effect. This resulted in higher glassy modulus
PUDIE-1

0.54
for PUSUL-1, PUMET-1, and PUDIS-1.57 SUL

Colourless

15.8
71.1

34.4
4.9
176.2
173.9

70
diol selectively increases the cohesion of the hard
segments and thereby dramatically modifies
the room temperature mechanical behavior as
shown in Table 2. Therefore, the elegant balance
between phase separation and phase mixing is
1,2-Propane

Colourless
PUPD-1

the most important criterion for the determi-

1.18
17.4
57.6

38.7
5.2
184.7
165.0

nation of overall sample mechanical properties.

90
diol

In the case of bulky diol chain extender PUDIE-1,

the formation of hard segment aggregation mor-
phology will be disturbed and results in lower
glassy modulus. The hard segment glass transi-
4,40 -Diamino-
PUMET-1

Pale yellow

tion temperature (TgH) was taken from the tan d

System

methane
diphenyl

182.4
202.0

17.6
74.6

35.2
8.4
2.6

curve, i.e. tan dmax value in the tensile mode

85
Table 2. Tensile and Dynamic Mechanical Properties of the Crosslinked Polyurethane-Ureas

experimentation. The higher value of TgH for

SUL among diamine chain extenders and for BD
among diol chain extenders suggests that the
phase separation of these MCPUs were more in
Pale yellow

comparison with other chain extender.58 The soft

disulfide
PUDIS-1

phenyl

8.7
1.4
170.3
175.5

15.4
67.2

32.7
4-Amino

segment glass transition was evaluated from the

78

first derivative of modulus versus temperature

plots, which showed a weak d(E0 )/dT transition
minima between 24 and 15 8C. These results
suggest the phase mixing characteristics.
4,40 -Diamino-
PUSUL-1

Pale yellow
diphenyl

22.6
81.6

47.5
11.8
1.7
220.4
208.5
sulfone

98

Thermal Properties
To investigate the morphological features, a
number of samples were subjected to DSC scan
with different time intervals and with different
extender

chain extenders, and the representative spectra

Colourless
PUIT-1

No chain

8.23
1.49
180.1
160.2

18.4
66.1

34.9

are shown in Figure 4. All the polyurethane

80

samples were subjected to identical thermal

treatment prior to recording DSC thermograms,
so that the thermal history of all materials was
identical. In case of segmented PUs, the pres-
TgH (8C)—hard segment, DMTA

ence of different crystal structures, domain

sizes, or different degree of order in the crystal-
Tensile strength (kgf/cm2)

line structure produces a number of DSC endo-

thermic peaks. But, the presence of a single
Tg (8C)—soft segment
E@ (106 Pa), at 25 8C
Chain Extender used

E0 (107 Pa), at 25 8C
Properties

broad endotherm as shown in Figure 4 indicates

that the crosslinking structure by the introduc-
Tmin (8C)—DSC
% Elongation

tion of triol reduced the accessibility of the hard

Appearance

segment distributed in the soft segment, and as

DH (J/g)

a consequence, these materials showed little

order. On the basis of Clough and Schneider’s59
interpretation, we could say that the broad
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU 111

Figure 4. DSC thermograms of the crosslinked PU-ureas with different chain

extenders.

endotherm was associated with the dissociation
of hard segment–soft segment hydrogen bonds.
However, the reports of Crawford et al.60 and
other researchers61–63 in the study on PUs sug-
gests that the endothermic transitions around
60–80 8C (endo I) and above 117 8C (endo II) are
associated with the breakdown of hydrogen bond-
ing between the polyurethane/urea–ether bonds
and in between the hard segments, respectively.
Studies on hydrogen bonding phenomenon by
Ren et al.64 and other associated studies65–68
could help us to interpret the broad endotherm
as the disruption of NHO¼ ¼C (type 1) and
NHCOC (type 2) hydrogen bonds. On a close
look of the enthalpy associated with this transi-
tion and that reported in Table 2, we could say
that the hydrogen bonding association was more
for PUSUL-1 and PUBD-1. This was due to the
use of polar SUL chain extender, which selec-
tively enhances hard segment cohesion and
thereby increases type 1 hydrogen bonding inter-
action. In case of PUBD-1, use of straight chain
diol could have resulted in strong interchain as-
sociation through hydrogen bonding interaction.
The minima in the enthalpy transition (Tmin) val-
ues are reported in Table 2.
The relative thermal stability of PU-urea
films was evaluated from the TGA data. The

Table 3. Thermal Stability Data of Polyurethane-Urea Systems

% wt Loss % wt Loss
System T1ON T2ON T1max T2max Tf at 300 8C at 450 8C

PUBD-1 310 385 366 397 424 7.25 93.2

PUPD-1 306 382 358 399 422 7.95 94.3
PUDIE-1 293 385 380 398 444 5.27 92.9
PUSUL-1 353 425 412 440 465 4.66 93.3
PUDIS-1 290 384 358 406 420.3 5.84 95.3
PUMET-1 330 401 397 423 445 8.15 90.3
PUIT-1 310 375 353 391 426 10.2 93.5
112 CHATTOPADHYAY, SREEDHAR, AND RAJU
Figure 5. TGA curves of different PU-urea films in nitrogen atmosphere.
values of T1ON (initial decomposition temperature
for the first step of decomposition), T2ON (initial
decomposition temperature for the second step of
decomposition), T1max (temperature of maximum
rate of weight loss for the first step), T2max (tem-
perature of maximum rate of weight loss for the
second step), Tf (final decomposition tempera-
ture), % weight loss at 300 and 450 8C, respec-
tively, are tabulated in Table 3. The correspond-
ing thermal stability curves in N2 environment
are shown in Figure 5. Following the initial deg-
radation in the hard segments, the second stage
of the degradation (T1ON) was related to the soft
segments and started after 290 8C, while the Tf
were in the range of 420–465 8C, which indicates
their good thermal stability.
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU 113

Figure 6. TGA curves of different PU-urea films in oxygen atmosphere.

The nature of the DTG curves showed the
complexity of the degradation following a num-
ber of steps of which two major steps are
involved. On a closer look on the thermal stabil-
ity of the coating systems (Table 3), it was found
that PUSUL-1 was most stable. The T1ON,
T1max, T2ON, T2max, and Tf values of PUSUL-1
were 353, 412, 425, 440, and 465 8C, respec-
tively, which is higher than those of the other
chain-extended PU-urea samples. PUMET-1 also
showed better stability in comparison with PU-
urea derived from diol chain extenders, and
this could be due to the presence of aromatic
ring in the chain extender and more urea bond
114 CHATTOPADHYAY, SREEDHAR, AND RAJU

concentration. Though PUDIS-1 contains aro-

matic ring in the chain extender, but its lower
stability in comparison with PUSUL-1 and
PUMET-1 (Table 3) may be due to the presence
of weak sulfur–sulfur (SS) bond or divalent
sulfur (SII). The excellent stability of PUSUL-1 is
due to the presence of strong resonant aryl sul-
fone groups, and because of the hexavalent sul-
fur.35,68 The CSVI bond (PUSUL-1) is stronger
than the CSII bond, due to the more electron
affinity of SVI and more r-bonding orbital over-
lapping. PUBD-1 was more stable than PUPD-1,
which is attributed to the more phase separation
nature of PUBD-1 in comparison with PUPD-1.
Though initially PUDIE-1 degraded faster be-
cause of the two bulky ethyl group substitutions,
at high temperature it was more stable than
PUPD-1 and PUBD-1. TGA curves of different
polyurethane films in oxygen atmosphere are
shown in Figure 6. The T1ON values of PUDIS-1
were 210, 225, 232, and 253 8C at a heating rate
of 5, 10, 15, and 20 8C/min, respectively, as shown
in Figure 6(a). These results clearly suggest that
the thermooxidative stability is dependent on the
heating rate, and stability increased with increas- Figure 7. XRD patterns of PU-urea films with dif-
ing heating rate. Figure 6(b) compares thermooxi- ferent chain extenders.
dative stability of PUMET-1 with PUIT-1 with
the heating rate of 10 8C/min. The T1ON values of coatings have good tensile strength and are flexi-
PUMET-1 and PUIT-1 were 232 and 220 8C, ble enough to withstand the stress/strain or wear
respectively. The presence of rigid aromatic ring generated during the service condition. PUSUL-1
due to the use of MET chain extender could have shows better mechanical properties in terms
increased thermooxidative stability of PUMET-1 of % elongation (220.4%) and tensile strength
in comparison with PUIT-1. Figure 6(c) represents (208.5 kgf/cm2) than the other polymers. The dif-
the dependence of thermal stability in oxygen of ference in mechanical properties in comparison
PUSUL-1 with the heating rate. The T1ON values with other diamine chain-extended PU-urea is
of PUSUL-1 at 5, 10, 15, and 20 8C/min heating due to the more phase-separated nature for SUL
rate were 257, 282, 297, and 303 8C, respectively. chain-extended PU-urea. Greater polarity of SUL
These values in comparison with thermooxidative induces increased intermolecular interactions
stability of PUDIS-1 suggest the higher stability between NH and C¼ ¼O of hard segments and
of PUSUL-1 than PUDIS-1. The thermal stability hence greater phase separation.69,70 In a similar
data of the films also supports good crosslinking way, the higher % elongation of PUBD-1 (193.2%)
ability of the evaluated polymer systems. in comparison with other diol chain-extended PU-
urea suggests more phase separation behavior of
PUBD-1. The less tensile strength of the polyur-
Tensile Properties ethanes derived from diol chain extender (Table 2)
The tensile property of polyurethane-urea gener- shows less rigidity of these films. This could be
ally depends on intermolecular bonding and due to the presence of aliphatic carbons in the
interactions within hard segments. The tensile chain extender backbone and more urethane bond
and dynamic mechanical properties of polymers concentration.
are reported in Table 2, which shows the depend-
ency of mechanical properties on the nature of
X-ray Diffraction
chain extender used. A primary concern was to
ensure that all samples were tested under identi- Figure 7 represents XRD curves of the PU-urea
cal conditions for internal consistency. All the films with different chain extender. For segmented
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU 115

Figure 8. Deconvoluted high-resolution C 1s spectra of (a) PUDIS-1, (b) PUMET-1,

(c) PUBD-1, and (d) PUSUL-1at takeoff angles 808 and 08.

block copolymers, the soft segments provide crys-
tallinity, unless the polymers have been an-
nealed.71 For a chemically crosslinked system,
the CLA (TMP) disrupts the regularity of the
hard segment and its packing into crystalline
regions in a regular fashion with the result
demolishes the regularity of the hard segment
and hence the crystallinity. Moreover, the as-
ymmetric nature of IPDI makes these materials
less crystalline. Therefore, these polymers be-
have as partially crystalline, and the most pro-
nounced maxima occurs at 2h  208. Figure 7
shows that PUBD-1 was more phase separated
among different diol chain extenders and PUSUL-1
was more phase separated in comparison with other
diamine chain extenders.
XPS Analysis
A pass energy of 80 eV was used for survey spec-
tra, which indicates peaks at 535, 400, 285, and
102 eV due to oxygen (1s), nitrogen (1s), carbon
(1s), and silicon (1s), respectively. Si is suspected
116 CHATTOPADHYAY, SREEDHAR, AND RAJU
Table 4. Contribution in Percentage of Different Functions to the Integrated Peak Area in the Deconvoluted
XPS Spectra at 08 and 808 Takeoff Angles
C 1s C 1s
Sample Angle (8) C/C
(C H) O:ether gr.)
(C
PUDIS-1 80 68.9 20.7
0 68.4 17.8
PUSUL-1 80 29.5 55.2
0 61.5 20.5
PUBD-1 80 42.6 42.9
0 60.3 18.2
PUMET-1 80 41.6 47.4
0 58.7 28.1
to be derived from dimethylsiloxane-based con-
taminants as reported earlier.72
As nitrogen is associated with the urethane
and urea linkages, the XPS elemental composi-
tion data (not shown) suggests a significant
increase in nitrogen concentration from the sur-
face to bulk, which signifies that the urethane
and urea content at the upper surface is much
less than in the bulk.73 The high-resolution C 1s
spectra as observed from the XPS analysis were
resolved into four characteristic peaks. The
observed peak at 284.6, 285.8–286.4, 287.0, and
289.0 eV are attributed to the functional groups
of C C/CH, CO, NHC(¼ ¼O)NH
and NHC(¼ ¼O) O, respectively, on the
surface of the PU-urea film. Deconvoluted high-
resolution C 1s spectra of (a) PUDIS-1, (b)
PUMET-1, (c) PUBD-1, and (d) PUSUL-1 at
takeoff angles 808 and 08 are shown in Figure 8.
A significant increase in peak area in the
binding energy peak at 286.0 eV was found for
all the analyzed samples on the surface (takeoff
angle 808), which suggests that the ether groups
preferentially resides toward the top surface of
the polymer. The contribution of different func-
tions to the integrated peak area in the deconvo-
luted XPS spectra of the representative systems
at 0 and 808 takeoff angles are shown in Table 4.
The CO (808)/CO (08) ratio for PUSUL-1,
PUMET-1, and PUDIS-1 were 2.69, 1.68, and
1.16. The higher CO (808)/CO (08) ratio
for PUSUL-1 suggests more localize nature of
the soft PEG segment toward the surface and
thereby more phase separation behavior among
the diamine chain-extended PU-urea. Similarly,
for PUBD-1, the CO (808)/CO (08) ratio was
2.35, much higher than that of the other diol
chain-extended PU-urea, suggests its superior
phase separation behavior in comparison with
CO C 1s C 1s
O (08)
(808)/C (from urea) (from urethane)
1.16 4.2 6.2
6.8 7.0
2.69 11.6 3.7
12.8 5.2
2.35 9.5 5.0
13.5 8.0
1.68 6.8 4.2
7.5 5.7
other diol chain-extended PU-urea. From Table 4,
we can see that the contribution from urea as
well as urethane functions to the total C 1s in-
tegrated peak were increased with decreasing
takeoff angle for all the representative samples.
These observations suggest the surface segrega-
tion nature of polyether segment toward the sur-
face and urethane/urea functions toward the bulk
and away from the surface. The enrichment of
soft segments at the air–polymer interface and
hard segments toward the bulk and away from
the surface is due to the lower air–polymer in-
terfacial energy of the soft segment relative to
the hard segment.37,73 The high resolution O 1s
XPS spectra are consistent overall with the C 1s
profiles and comprised mainly of CO (531.5–
532.5 eV) and C¼¼O moieties (532–534.5 eV). The
more microphase-separated material provides a
higher driving force for soft segments to localize
on the surface because of increase in the mobility
of the soft segments. These results confirms that
the surface composition of a multicomponent
PU-urea differs substantially from the bulk com-
position and the phenomenon is associated with
the surface energy, the surface being enriched
with lower energy components.
CONCLUSIONS
An experimental investigation was undertaken
to study the physical properties of chemically
crosslinked moisture-cured PU-urea with a var-
iation in chain extender structure. The cure be-
havior was monitored by evaluating change of
modulus (E0 ) at 40 8C. The replacement of diol
chain extenders by diamines has resulted in
different properties. The glassy state modulus
values at low temperature showed polyurethane
 PROPERTIES OF CHEMICALLY CROSSLINKED MCPU
with diamine chain extender posses more hard-
ness than diols. The thermal stability data
showed highest stability of PUSUL-1 and lowest
stability of PUDIS-1 among diamine chain ex-
tenders. PUSUL-1 also showed better mechani-
cal properties in comparison with other poly-
mers. The soft segment glass transition was not
observed from DSC; however, a weak transition
centered between 24 and 15 8C was observed
from the first derivative curve of modulus versus
temperature plots in DMTA, and was related to
the soft segment glass transition. The DSC result
showed a broad endothermic peak between 50
and 120 8C. FTIR studies, XRD curves, and
enthalpy data showed that PUBD-1 and PUSUL-
1 were more phase separated. Surface segrega-
tion phenomenon of soft segment was confirmed
by AR-XPS.
One of the authors, DKC, acknowledges the Univer-
sity Grants Commission, India for the financial sup-
port in the form of a research fellowship.
REFERENCES AND NOTES
1. Oprea, S.; Oprea, V. Eur Polym J 2002, 38, 1205.
2. Petrovic, Z. S.; Ilavsky, M.; Dusek, K.; Vidakovic,
M.; Javni, I.; Banjanin, B. J Appl Polym Sci 1991,
42, 391.
3. Chang, W.; Baranowski, T.; Karalis, T. J Appl
Polym Sci 1994, 51, 1077.
4. Petrovic, Z. S.; Javni, I.; Divjakovic, V. J Polym
Sci Part B: Polym Phys 1998, 36, 221.
5. Kontou, E.; Spathis, G.; Niaounakis, M.; Kefalas,
V. Colloid Polym Sci 1990, 268, 636.
6. Krakovsky, I.; Bubennykova, Z.; Urakawa, H.;
Kajiwara, K. Polymer 1997, 38, 3637.
7. Krakovsky, I.; Urakawa, H.; Kajiwara, K. Polymer
1997, 38, 3645.
8. Smith, T. L.; Magnusson, A. B. J Appl Polym Sci
1961, 5, 218.
9. Haska, S. B.; Bayramli, E.; Pekel, F.; Ozkar, S.
J Appl Polym Sci 1997, 64, 2347.
10. Kothandaraman, H.; Venkatarao, K.; Thanoo,
B. C. Polym J 1989, 21, 829.
11. Kothandaraman, H.; Venkatarao, K.; Thanoo,
B. C. J Appl Polym Sci 1990, 39, 943.
12. Consaga, J. P.; French, D. M. J Appl Polym Sci
1971, 15, 2941.
13. Spirkova, M.; Matejka, L.; Hlavata, D.; Meissner,
B.; Pytela, J. J Appl Polym Sci 2000, 77, 381.
14. Desai, S.; Thakore, I. M.; Sarawade, B. D.; Devi,
S. Eur Polym J 2000, 36, 711.
15. Smith, T. L.; Magnusson, A. B. J Polym Sci 1960,
42, 391.
117
16. Paulmer, R. D. A.; Shah, C. S.; Patni, M. J.; Pan-
dya, M. V. J Appl Polym Sci 1991, 43, 1953.
17. Jung, H. C.; Kang, S. J.; Kim, W. N.; Lee, Y.-B.;
Choe, K. H.; Hong, S.-H.; Kim, S.-B. J Appl
Polym Sci 2000, 78, 624.
18. Cooper, S. L.; Tobolsky, A. V. J Appl Polym Sci
1967, 11, 1361.
19. Dzierza, W. J Appl Polym Sci 1978, 22, 1331.
20. Sasaki, N.; Yokoyama, T.; Tanaka, T. J Polym Sci
Polym Chem Ed 1973, 11, 1765.
21. Nierzwicki, W.; Wysocka, E. J Appl Polym Sci
1980, 25, 739.
22. Buckley, L. J.; Hammond, P. T.; Rubner, F. M.
Macromolecules 1993, 26, 2380.
23. Nallicheri, R. A.; Rubner, M. F. Macromolecules
1990, 23, 1017.
24. Lee, H. S.; Hsu, S. L. J Polym Sci Part B: Polym
Phys 1994, 32, 2085.
25. Foks, J.; Janik, H.; Russo, R.; Winiecki, S. Eur
Polym J 1989, 25, 31.
26. Brunette, C. M.; Hsu, S. L.; Rossman, M.; Mac-
Knight, W. J.; Schneider, N. S. Polym Eng Sci
1981, 21, 668.
27. Camberlin, Y.; Pascult, J. P. J Polym Sci Polym
Chem Ed 1983, 21, 415.
28. Wagener, K. B.; Matayabas, J. C., Jr.; Wanigatunga,
S. Macromolecules 1989, 22, 3211.
29. Vilensky, V. A.; Lipatov, Y. S. Polymer 1994, 35,
3069.
30. Kanapitsas, A.; Pissis, P.; Gomez Ribelles, J. L.;
Monleon Pradas, M.; Privalko, E. G.; Privalko,
V. P. J Appl Polym Sci 1999, 71, 1209.
31. Yoo, S. R.; Lee, H. S.; Seo, S. W. Polymer (Korea)
1997, 21, 467.
32. Lee, Y. M.; Lee, J. C.; Kim, B. K. Polymer 1994,
35, 1095.
33. Wang, F. C.; Feve, M.; Lam, T. M.; Pascault, J. P.
J Polym Sci Part B: Polym Phys 1994, 32, 1305.
34. Coleman, M. M.; Lee, K. H.; Skrovanek, D. J.;
Painter, P. C. Macromolecules 1986, 19, 2149.
35. Chattopadhyay, D. K.; Sreedhar, B.; Raju, K. V.
S. N. J Appl Polym Sci 2005, 95, 1509.
36. Chattopadhyay, D. K.; Sreedhar, B.; Raju, K. V.
S. N., submitted to Polymer.
37. Chattopadhyay, D. K.; Sreedhar, B.; Raju, K. V.
S. N. Ind Eng Chem Res 2005, 44, 1772.
38. Lomolder, R.; Plogmann, F.; Speier, P. J Coat
Technol 1997, 69(868), 51.
39. Ludwig, B. W.; Urban, M. W. J Coat Technol
1994, 66(839), 59.
40. Kaminski, A. M.; Urban, M. W. J Coat Technol
1997, 69(873), 113.
41. Ludwig, B. W.; Urban, M. W. J Coat Technol
1996, 68(857), 93.
42. Dearth, R. S.; Mertes, H.; Jacobs, P. J. Prog Org
Coat 1996, 29, 73.
43. Cui, Y.; Chen, D.; Wang, X.; Tang, X. Int J Adhes
Adhes 2002, 22, 317.
44. Koscielecka, A. Acta Polym 1991, 42, 221.
118 CHATTOPADHYAY, SREEDHAR, AND RAJU
45. Kordomenos, P. I.; Kresta, J. E.; Frisch, K. C.
Macromolecules 1987, 20, 2077.
46. Dusek, K.; Spirkova, M.; Havlicek, I. Macromole-
cules 1990, 23, 1774.
47. Petrovic, Z. S.; Javni, I. J Polym Sci Part B:
Polym Phys 1989, 27, 545.
48. Deslandes, Y.; Pleizer, G.; Alexander, D.; San-
terre, P. Polymer 1998, 39, 2361.
49. Prabhakar, A.; Chattopadhyay, D. K.; Jagadeesh,
B.; Raju, K. V. S. N. J Polym Sci Part A: Polym
Chem 2005, 43, 1196.
50. Awater, A. In Polyurethane Handbook, Oertel, G.,
Ed.; Hanser Publishers: Munich, 1985; p 378.
51. Duff, D. W.; Macial, G. E. Macromolecules 1991,
24, 387.
52. Prisacariu, C.; Agherghinei, I. J Macromol Sci
Pure Appl Chem 2000, 37, 785.
53. Queiroz, D. P.; Pinho, M. N.; de Dias, C. Macro-
molecules 2003, 36, 4195.
54. Cocca, M.; Darienzo, L.; Dorazio, L.; Gentile, G.;
Martuscelli, E. J Polym Sci Part B: Polym Phys
2005, 43, 542.
55. Romanova, V.; Begishev, V.; Karmanov, V.;
Kondyurin, A.; Maitz, M. F. J Raman Spectrosc
2002, 33, 769.
56. Chattopadhyay, D. K.; Prasad, P. S. R.; Raju,
K. V. S. N.; under preparation.
57. Wang, C. B.; Cooper, S. L. Macromolecules 1983,
16, 775.
58. Delpech, M. C.; Coutinho, F. M. B. Polym Test
2000, 19, 939.
59. Clough, S. B.; Schneider, N. S. J Macromol Sci B
Phys 1968, 2, 553.
60. Crawford, D. M.; Bass, R. G.; Haas, T. W.
Thermochim Acta 1998, 323, 53.
61. Saymour, R. W.; Cooper, S. L. Macromolecules
1973, 6, 48.
62. Seymour, R.; Cooper, S. J Polym Sci Part B:
Polym Lett 1971, 9, 689.
63. Leung, L. M.; Koberstein, J. T. Macromolecules
1986, 19, 706.
64. Ren, Z.; Ma, D.; Yang, X. Polymer 2003, 44, 6419.
65. Lee, H. S.; Wang, Y. K.; Hsu, S. L. Macromole-
cules 1987, 20, 2089.
66. Tanaka, T.; Yokoyama, T.; Yamaguchi, Y. J Polym
Sci 1968, 6, 2137.
67. Coleman, M. M.; Skrovanek, D. J.; Hu, J. B.;
Painter, P. C. Macromolecules 1988, 21, 59.
68. Filip, D.; Macocinschi, D. Polym Int 2002, 51,
699.
69. Liaw, D. J. J Appl Polym Sci 1997, 66, 1251.
70. Zhang, T.; Litt, M. H.; Rogers, C. E. J Polym Sci
Part B: Polym Phys 1994, 32, 1671.
71. Kovacevic, V.; Smith, I.; Hace, D.; Suceska, M.;
Mundri, I.; Bravar, M.; Int J Adhes Adhes 1993,
13, 126.
72. Sidouni, F. Z.; Nurdin, N.; Chabrecek, P.; Loh-
mann, D.; Vogt, J.; Xanthopoulos, N.; Mathieu, H.
J.; Francois, P.; Vaudaux, P.; Descounts, P. Surf
Sci 2001, 491, 355.
73. Wang, G. B.; Labow, R. S.; Santerre, J. P. Macro-
molecules 2000, 33, 7321.